EP3369777B1 - Polybutylenterephthalat-harzzusammensetzung - Google Patents

Polybutylenterephthalat-harzzusammensetzung Download PDF

Info

Publication number
EP3369777B1
EP3369777B1 EP16859858.9A EP16859858A EP3369777B1 EP 3369777 B1 EP3369777 B1 EP 3369777B1 EP 16859858 A EP16859858 A EP 16859858A EP 3369777 B1 EP3369777 B1 EP 3369777B1
Authority
EP
European Patent Office
Prior art keywords
polybutylene terephthalate
terephthalate resin
resin composition
mass
molded article
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP16859858.9A
Other languages
English (en)
French (fr)
Other versions
EP3369777A4 (de
EP3369777A1 (de
Inventor
Shinya Yamada
Kouichi Sakata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polyplastics Co Ltd
Original Assignee
Polyplastics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polyplastics Co Ltd filed Critical Polyplastics Co Ltd
Priority to PL16859858T priority Critical patent/PL3369777T3/pl
Publication of EP3369777A1 publication Critical patent/EP3369777A1/de
Publication of EP3369777A4 publication Critical patent/EP3369777A4/de
Application granted granted Critical
Publication of EP3369777B1 publication Critical patent/EP3369777B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming

Definitions

  • the present invention relates to a polybutylene terephthalate resin composition, and more specifically relates to a polybutylene terephthalate resin composition for forming a molded article having a lightness L* value of 80 or more as measured with a color difference meter.
  • Polybutylene terephthalate resins which have excellent mechanical, electrical, and other physical and chemical properties as well as good processability, are used as engineering plastics for a wide range of uses such as electrical/electronic components. Further, polybutylene terephthalate resins may be blended with fibrous bulking agents such as glass fiber to produce resin compositions for forming reinforced molded articles having improved thermal resistance and strength.
  • Such polybutylene terephthalate resins often find their uses, for example, as housing materials for sensors and/or ECUs used for electric control in the automotive field.
  • these articles are often alloyed with an amorphous resin such as polycarbonate, or mixed with an inorganic bulking agent in a form of a high-aspect ratio flake or power.
  • toughness may often be improved by blending an elastomer or the like in order to prevent the occurrence of a crack due to strain arising from difference in linear expansion between metal and resin.
  • a large amount of an elastomer required to be blended for obtaining sufficient heat shock resistance may cause a problem of a decrease in strength.
  • a system alloyed with an amorphous resin such as polycarbonate or mixed with an inorganic bulking agent in a form of a high-aspect ratio flake or power in order to achieve low warpage as described above tends to show decreased heat shock resistance.
  • Patent Document 1 proposes a polybutylene terephthalate resin composition in which a specific amount of a carbodiimide compound is blended in a polybutylene terephthalate resin.
  • the above resin composition can confer excellent heat shock resistance on a molded article.
  • a carbodiimide compound blended in a polybutylene terephthalate resin as described above is widely known to be able to improve hydrolysis resistance.
  • a molded article formed from a polybutylene terephthalate resin composition in which a carbodiimide compound is blended in a polybutylene terephthalate resin is used under a high-temperature environment
  • carbodiimide may undergo heat-induced yellow discoloration.
  • the molded article may suffer from discoloration.
  • the color of an automotive component for which heat shock resistance is required is usually black.
  • the product value of a pale-colored molded article would be significantly reduced due to discoloration.
  • a phosphorus-based stabilizer and the like may be added to prevent heat-induced discoloration, but will interfere with an improving effect on heat shock resistance.
  • Patent Document 1 PCT International Publication No. WO 2009/150833
  • An object of the present invention is to provide a polybutylene terephthalate resin composition capable of preventing discoloration effectively without reducing heat shock resistance.
  • the present investors found that heat-induced discoloration can be prevented while maintaining excellent heat shock resistance by blending a carbodiimide compound and a specific amount of a phosphite-based compound with a polybutylene terephthalate resin having a terminal-carboxyl group content of 30 meq/kg or less.
  • the present invention was then completed. That is, the present invention can provide the following.
  • the present invention can provide a polybutylene terephthalate resin composition capable of preventing discoloration effectively without reducing heat shock resistance.
  • Fig. 1 is a graph showing the measurement results of hue b* values versus the time of cold and heat treatment at 120°C from Example and Comparative Examples.
  • the polybutylene terephthalate resin composition (hereinafter may also be simply referred to the "resin composition") according to an embodiment of the present invention may be used to form a molded article having a lightness L* value of 80 or more as measured with a color difference meter, and in particular may be used to form a molded article for which heat shock resistance is required, such as an automotive component and/or an electric/electronic component.
  • the above polybutylene terephthalate resin composition includes a polybutylene terephthalate resin (A) and an aromatic carbodiimide compound (B). Further, the polybutylene terephthalate resin composition according to an embodiment of the present invention is characterized in that a specific amount of a phosphite-based compound is contained in a resin composition including the polybutylene terephthalate resin and the carbodiimide compound.
  • a molded article formed from a polybutylene terephthalate resin composition having excellent mechanical, electrical, or other physical and chemical properties is often used as a molded article of an automobile component and the like, and is further used under an environment experiencing intense temperature rises and falls. Therefore, a carbodiimide compound is contained to improve heat shock resistance.
  • a molded article obtained from a polybutylene terephthalate resin composition including a carbodiimide compound as described above may disadvantageously undergo heat-induced discoloration to yellow or other colors. Further, the discoloration problem becomes more significant as the lightness of the molded article increases, for example, as the lightness L* value of the molded article increases to 80 or more as measured with a color difference meter. This is a factor that reduces the product value of the molded article.
  • a polybutylene terephthalate resin as a basis resin of the resin composition according to an embodiment of the present invention is a polybutylene terephthalate-based polymer which may be obtained by performing polycondensation of a dicarboxylic-acid component including at least terephthalic acid or an esterified derivative thereof (a lower alcohol ester and the like) and a glycol component including at least alkylene glycol having 4 carbon atoms (1,4-butanediol) or an esterified derivative thereof.
  • the polybutylene terephthalate resin is not limited to a homo-polybutylene terephthalate resin, but may be, for example, a copolymer including butylene terephthalate units in a percentage of 60 mol% or more (in particular, about 75 to 95 mol%) .
  • the polybutylene terephthalate resin may have a terminal-carboxyl group content of 30 meq/kg or less, preferably 25 meq/kg or less.
  • the terminal-carboxyl group content may be, for example, measured as follows. That is, a sample of grounded polybutylene terephthalate may be dissolved in benzyl alcohol under a temperature condition of 215°C for 10 minutes, and then titrated with 0.01 N of aqueous sodium hydroxide to determine the content.
  • a polybutylene terephthalate resin having a terminal-carboxyl group content of more than 30 meq/kg will reduce the improving effect on heat shock resistance regardless of the addition amount of a carbodiimide compound described below. Further, the strength may be significantly decreased due to hydrolysis under a high-temperature and moist environment.
  • the terminal-carboxyl group content of the polybutylene terephthalate resin is preferably 5 meq/kg or more, more preferably 10 meq/kg or more.
  • the intrinsic viscosity (IV) of the polybutylene terephthalate resin is preferably 0.65 dL/g or more to 1.20 dL/g or less, more preferably 0.75 dL/g or more to 1.0 dL/g or less.
  • An intrinsic viscosity in the range of 0.65 dL/g or more to 1.20 dL/g or less tends to provide a fluidity required for molding, for example, an insert molded article.
  • polybutylene terephthalate resins having different intrinsic viscosities may be blended to obtain a polybutylene terephthalate resin having a desired intrinsic viscosity.
  • a polybutylene terephthalate resin having an intrinsic viscosity of 1.00 dL/g may be blended with a polybutylene terephthalate resin having an intrinsic viscosity of 0.70 dL/g to obtain a polybutylene terephthalate resin having an intrinsic viscosity of 0.90 or less.
  • the intrinsic viscosity can be measured, for example, in o-chlorophenol under a temperature condition of 35°C.
  • Dicarboxylic acid components (comonomer components) other than terephthalic acid and an esterified derivative thereof in the polybutylene terephthalate resin include, for example, aromatic dicarboxylic acid components (C6-C12 aryl dicarboxylic acid and the like such as isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and diphenyl ether dicarboxylic acid), aliphatic dicarboxylic acid components (C4-C16 alkyl dicarboxylic acid such as succinic acid, adipic acid, azelaic acid, and sebacic acid, and C5-C10 cycloalkyl dicarboxylic acid such as cyclohexanedicarboxylic acid), esterified derivatives thereof, or the like. These dicarboxylic acid components may be used alone or in a combination of two or more.
  • aromatic dicarboxylic acid components C6-C12 aryl dicarboxylic acid
  • preferred dicarboxylic acid components include aromatic dicarboxylic acid components (in particular, C6-C10 aryl dicarboxylic acid such as isophthalic acid) and aliphatic dicarboxylic acid components (in particular, C6-C12 alkyl dicarboxylic acid such as adipic acid, azelaic acid, and sebacic acid).
  • aromatic dicarboxylic acid components in particular, C6-C10 aryl dicarboxylic acid such as isophthalic acid
  • aliphatic dicarboxylic acid components in particular, C6-C12 alkyl dicarboxylic acid such as adipic acid, azelaic acid, and sebacic acid.
  • Glycol components (comonomer components) other than 1,4-butanediol include, for example, aliphatic diol components [for example, alkylene glycol (C2-C10 alkylene glycol such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, 1,3-octanediol; polyoxy C2-C4 alkylene glycol such as diethylene glycol, triethylene glycol, and dipropylene glycol; and the like), alicyclic diol such as cyclohexane dimethanol and hydrogenated bisphenol A, and the like]; aromatic diol components [aromatic alcohol such as bisphenol A and 4,4-dihydroxybiphenyl; C2-C4 alkylene oxide adduct of bisphenol A and the like (for example, 2-mol ethylene oxide adduct of bisphenol A, 3-mol propylene oxide adduct of
  • glycol components include aliphatic diol components (in particular, C2-C6 alkylene glycol, polyoxy C2-C3 alkylene glycol such as diethylene glycol, and alicyclic diol such as cyclohexanedimethanol).
  • aliphatic diol components in particular, C2-C6 alkylene glycol, polyoxy C2-C3 alkylene glycol such as diethylene glycol, and alicyclic diol such as cyclohexanedimethanol.
  • polybutylene terephthalate-based polymers obtainable by polycondensation of the aforementioned compounds as monomer components may be suitably used as a polybutylene terephthalate resin component of the polybutylene terephthalate resin composition. Further, a combination of a homo-polybutylene terephthalate polymer and a polybutylene terephthalate copolymer is also useful.
  • the resin composition according to an embodiment of the present invention includes an aromatic carbodiimide compound blended with the aforementioned polybutylene terephthalate resin.
  • an aromatic carbodiimide compound as described above can improve heat shock resistance, enabling, for example, the occurrence of a crack and the like due to strain arising from a difference in linear expansion to be effectively prevented even in an environment experiencing intense temperature rises and falls. Further, hydrolysis resistance can also be improved to reduce decomposition of a resin component and the like, preventing a decrease in strength.
  • Carbodiimide compounds include an aliphatic carbodiimide compound in which the main chain is aliphatic, an alicyclic carbodiimide compound in which the main chain is alicyclic, an aromatic carbodiimide compound in which the main chain is aromatic, and the like. According to the present invention, the aromatic carbodiimide compound is used considering that the improving effects on heat shock resistance and hydrolysis resistance are superior.
  • Aromatic carbodiimide compounds include mono- or di-carbodiimide compounds such as diphenylcarbodiimide, di-2,6-dimethylphenyl carbodiimide, N-triyl-N'-phenylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorphenylcarbodiimide, di-p-methoxyphenycarbodiimide, di-3,4-dichlorphenylcarbodiimide, di-2,5-dichlorphenylcarbodiimide, di-o-chlorphenylcarbodiimide, p-phenylene-bis-di-o-triylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-di-p-chlorphenyl
  • di-2,6-dimethylphenylcarbodiimide, poly(4,4'-diphenylmethanecarbodiimide), poly(phenylenecarbodiimide), and poly(triisopropylphenylenecarbodiimide) are in particular suitably used. It is noted that these may be used alone or in a combination of two or more.
  • aromatic carbodiimide compound there is no particular limitation on the aromatic carbodiimide compound, but those having a molecular weight of 2000 or more are preferably used. Those having a molecular weight of less than 2000 may generate a gas or an odor, for example, when residence time is long in melt kneading and molding.
  • the blending amount of a carbodiimide compound in the polybutylene terephthalate resin composition is preferably 0.01 parts by mass or more to 5.0 parts by mass or less per 100 parts by mass of the polybutylene terephthalate resin (A), more preferably 0.1 parts by mass or more to 3.0 parts by mass or less, and even more preferably 0.3 parts by mass or more to 2.5 parts by mass or less.
  • the blending amount of a carbodiimide compound is less than 0.01 parts by mass, the improving effect on heat shock resistance may not sufficiently be obtained. Further, the effect of hydrolysis resistance may not be sufficiently obtained, either.
  • a blending amount of more than 5.0 parts by mass may tend to decrease fluidity and/or generate a gel component and/or carbide upon a compounding and/or molding process, resulting in decreased machinery properties such as tensile strength and bending strength. Further, the yield of isocyanate gas originating from a carbodiimide compound may be increased, resulting in a poor work environment.
  • the polybutylene terephthalate resin composition according to an embodiment of the present invention includes a phosphite-based compound so that the content thereof is 0.05 parts by mass or more to 0.12 parts by mass or less per 100 parts by mass of a polybutylene terephthalate resin.
  • the polybutylene terephthalate resin composition according to an embodiment of the present invention includes a specific amount of a phosphite-based compound as described above. This can effectively prevent heat-induced discoloration of a molded article without impairing the improving effect on heat shock resistance by virtue of the inclusion of a carbodiimide compound.
  • phosphite-based compounds include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecylmonophenyl phosphite, dioctylmonophenyl phosphite, diisopropylmonophenyl phosphite, monobutyldiphenyl phosphite, monodecyldiphenyl phosphite, monooctyldiphenyl phosphite, tris(diethylphenyl)phosphite, tris(di-isopropylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butyl
  • the content of a phosphite-based compound is 0.05 parts by mass or more to 0.12 parts by mass or less per 100 parts by mass of a polybutylene terephthalate resin.
  • it is 0.08 parts by mass or more to 0.12 parts by mass or less per 100 parts by mass of a polybutylene terephthalate resin.
  • a content of less than 0.05 parts by mass would not be able to sufficiently prevent heat-induced discoloration.
  • a content of more than 0.12 parts by mass may reduce the heat shock resistance and hydrolysis resistance of a molded article.
  • a polybutylene terephthalate resin composition is alloyed by including a polyester resin other than a polybutylene terephthalate resin, such as a polycarbonate resin and/or a polyethylene terephthalate resin, in a polybutylene terephthalate resin as the main component for the purpose of preventing warpage deformation and the like.
  • a phosphorus compound is commonly added to such a polybutylene terephthalate resin composition alloyed with a polyester resin to allow the phosphorus compound to act as a transesterification inhibitor, thereby inhibiting a transesterification reaction between a polybutylene terephthalate resin and the alloy resin.
  • the polybutylene terephthalate resin composition according to an embodiment of the present invention preferably includes neither a polycarbonate resin, a polyethylene terephthalate resin, nor the like, i.e., is preferably not alloyed. Therefore, the phosphite-based compound (C) differs from a phosphorus compound as a transesterification inhibitor to be added for inhibiting transesterification.
  • the polybutylene terephthalate resin composition according to an embodiment of the present invention may include a bulking agent as an additive.
  • a bulking agent as an additive.
  • the inclusion of a bulking agent in a resin composition can enhance mechanical strength and/or stiffness.
  • Bulking agents include fibrous bulking agents or non-fibrous bulking agents in platelike, powderlike, spherical, or other forms.
  • Fibrous bulking agents include glass fiber, carbon fiber, potassium-titanate fiber, silica-alumina fiber, zirconia fiber, metal fiber, organic fiber, and the like. Among these, glass fiber is preferably used.
  • any known types of glass fiber may be preferably used.
  • the diameter and cross-sectional shape of glass fiber and any of cylinder-like, cocoon-like, and ellipse-like cross-sections may be used.
  • the length and method of cutting glass for manufacturing chopped strands, rovings, and the like are also no particular limitation on the type of glass, but the E glass and/or an anticorrosion glass containing elemental zirconium in the composition are suitably used in view of quality.
  • a fibrous bulking agent which is surface-treated with an organic treatment agent such as an aminosilane compound and an epoxy compound may suitably be used in order to improve interface properties between the fibrous bulking agent and a resin.
  • an organic treatment agent such as an aminosilane compound and an epoxy compound
  • the aminosilane compound and the epoxy compound which may be used for the aforementioned fibrous bulking agent, and any known agent may be used.
  • Non-fibrous bulking agents include talc, mica, glass flakes, glass beads, calcium carbonate, and the like. Among these, talc and mica are preferred.
  • the blending amount of a bulking agent in the resin composition is preferably 0 part by mass or more to 100 parts by mass or less per 100 parts by mass of the polybutylene terephthalate resin (A), more preferably 10 parts by mass or more to 50 parts by mass or less per 100 parts by mass of the polybutylene terephthalate resin (A).
  • a blending amount falling within the above range can improve mechanical properties without impairing moldability.
  • the polybutylene terephthalate resin composition according to an embodiment of the present invention may include a known substance which is generally added to a thermoplastic resin, a thermosetting resin, and the like in order to further confer a desired property depending on the purpose.
  • a stabilizer such as an antioxidant, a heat-resistant stabilizer, and an ultraviolet absorber
  • an antistatic agent such as an antioxidant, a heat-resistant stabilizer, and an ultraviolet absorber
  • a coloring agent such as a dye and a pigment
  • a plasticizing agent such as a plasticizing agent
  • a flow improver a crystallization accelerator
  • a crystal nucleating agent such as an epoxy compound
  • a lubricating agent a release agent
  • the polybutylene terephthalate resin composition according to an embodiment of the present invention can be easily prepared using a common facility and method as in a method of preparing a conventional resin composition.
  • each of the components of the resin composition may be mixed, and kneaded with a single or twin screw extruder or a melt kneader of a different type to prepare moldable pellets. Multiple extruders or melt kneaders of different types may be used. All of the components may be simultaneously fed through a hopper, or some of the components may be fed through a side feeding inlet.
  • the temperature of an extruder cylinder is adjusted so that the resin temperature inside the extruder is preferably 240°C to 300°C, more preferably 250°C to 270°C.
  • the resin temperature is lower than 240°C, heat shock resistance and/or hydrolysis resistance may not sufficiently be obtained due to an insufficient reaction between a polybutylene terephthalate resin and a carbodiimide compound.
  • the resin temperature is higher than 300°C, the resin may tend to be more susceptible to decomposition.
  • the aromatic carbodiimide compound (B) of the resin composition may be, for example, blended as a masterbatch having a matrix of a resin.
  • a masterbatch prepared with a polybutylene terephthalate resin is suitably used, but those masterbatches prepared with other resins may also be used.
  • the blending amounts of the resin and a carbodiimide compound may be adjusted so as to fall within the predetermined ranges.
  • the masterbatch may be pre-introduced upon melt kneading to obtain uniformly mixed pellets.
  • the polybutylene terephthalate resin composition according to an embodiment of the present invention can confer excellent heat shock resistance and/or hydrolysis resistance on a molded article obtained by molding the resin composition. That is, the occurrence of a crack and the like due to strain arising from a difference in linear expansion can be effectively prevented even under an environment experiencing intense temperature rises and falls, and decomposition of resin components and the like can also be inhibited to prevent a decrease in strength and the like.
  • polybutylene terephthalate resin composition according to an embodiment of the present invention can effectively prevent heat-induced discoloration to yellow or other colors while maintaining heat shock resistance as described above.
  • a molded article obtained by molding this polybutylene terephthalate resin composition has heat shock resistance of 300 cycles or more as determined according to the heat shock test, and further has an increase in a hue b* value by 5 or less before and after treatment as measured with a color difference meter before and after cold and heat treatment of 120°C x 1000 hours. Further, the hue b* value after the cold and heat treatment of 120°C x 1000 hours is 10 or less.
  • the polybutylene terephthalate resin composition according to an embodiment of the present invention may be used to obtain a molded article having a lightness L* value of 80 or more as measured with a color difference meter as described above.
  • a molded article having such a relatively high lightness may show significant heat-induced discoloration to yellow or other colors.
  • discoloration is significant enough to be visually recognized.
  • heat-induced discoloration to yellow or other colors of the resulting molded article can be effectively prevented.
  • heat shock resistance can be evaluated according to the following heat shock resistance test. That is, a molded article such as an insert molded article formed from the resin composition is heated at 140°C for 1 hour and 30 minutes in a cold and heat shock testing machine, and then cooled to -40°C and maintained for 1 hour and 30 minutes, and then heated to 140°C again. This is considered as one cycle. Then, the number of cycles until a crack occurs in the molded article is determined. That number of cycles can be used to evaluate heat shock resistance.
  • the polybutylene terephthalate resin composition according to an embodiment of the present invention is particularly useful for forming a molded article, such as automotive components and the like, for use under an environment experiencing intense temperature rises and falls. It also can effectively prevent discoloration such as yellow discoloration while maintaining heat shock resistance, preventing a reduction of the product value of the molded article.
  • the pellets produced were subject to insert injection molding in a mold for forming a test piece (a mold in which an iron core of 18 mm in length and 18 mm in width and 30 mm in height is to be inserted inside a rectangular column of 22 mm in length and 22 mm in width and 51 mm in height) at a resin temperature of 260°C, a mold temperature of 65°C, an injection time of 25 seconds, and a cooling time of 10 seconds so that the minimum thickness of a part of a resin portion was 1 mm, thereby manufacturing an insert molded article.
  • a test piece a mold in which an iron core of 18 mm in length and 18 mm in width and 30 mm in height is to be inserted inside a rectangular column of 22 mm in length and 22 mm in width and 51 mm in height
  • the resulting insert molded article was subject to a heat shock resistance test with a cycle of heating at 140°C for 1 hour and 30 minutes in a cold and heat shock testing machine, and then cooling to -40°C and maintaining for 1 hour 30 minutes, and then heating to 140°C again.
  • the above test determined the number of cycles until a crack occurred in the molded article, thereby the heat shock resistance was evaluated.
  • the insert molded article obtained as described above was measured for color with a spectroscopic color difference meter from Nippon Denshoku Industries Co., Ltd. (SE6000, Nippon Denshoku Industries Co., Ltd.) in accordance with the method of measuring reflection on an object using a spectrophotometer defined in JIS Z 8722:2009. Based on the results from the above, the lightness L* value was calculated according to the CIE 1976 L*a*b* color space defined in JIS Z 8730-4:2013.
  • the insert molded article obtained as described above was heated at 120°C in a cold and heat shock testing machine, and measured for a hue b* value with a spectroscopic color difference meter (SE6000, Nippon Denshoku Industries Co., Ltd.) both before the cold and heat treatment and after 1000 hours. Further, an increase in a b* value before and after the cold and heat treatment (a value obtained by subtracting the b* value before the treatment from the b* value after the treatment) was calculated. It is noted that the b* value is an index of the degree of yellowness in the CIE 1976 L*a*b* color space defined in JIS Z 8781-4:2013. A smaller value means a smaller degree of yellow discoloration of a molded article. Therefore, a smaller difference between the b* values before and after the treatment means a smaller degree of yellow discoloration, representing a preferred result.
  • SE6000 spectroscopic color difference meter
  • Fig. 1 is a graph showing the measurement results of hue b* values versus the time of cold and heat treatment at 120°C from Example 1 and Comparative Examples 4, 5, and 7.
  • [Table 1] Components of resin composition [ Parts by mass] Example Comparative Example 1 1 2 3 4 5 6 7
  • A PBT resin A-1 100 100 100 100 100 100 100 100 100 100 100 (B) Carbodiimide compound B-1 0.8 0.8 0.8 0.8 0.8 0.8 (C) Phosphite-based compound C-1 0.1 - 0.03 0.2 - - - - (C') Other phosphorus compounds C'-1 0.1 C'-2 0.04 0.1 C'-3 0.1
  • D Glass fiber D-1 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 43 Heat shock resistance (Cycles) 330 336 335 271 237 353 93 266 Lightness L* value 92.58 92.52 92.54 92.60 92.03 90.07 - 91.42
  • a molded article prepared from a polybutylene terephthalate resin composition in which a phosphite-based compound was added to a resin composition including a polybutylene terephthalate resin and a carbodiimide compound showed reduced discoloration with a small difference in hue b* values after the cold and heat treatment while maintaining excellent heat shock resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (4)

  1. Polybutylen-Terephthalat-Harzzusammensetzung zur Bildung eines Formgegenstandes mit einem Helligkeitswert L* von 80 oder mehr, wie mit einem Farbdifferenzmesser gemessen, wobei die Polybutylen-Terephthalat-Harzzusammensetzung umfasst:
    ein Polybutylen-Terephthalat-Harz mit einem Gehalt an endständigen Carboxylgruppen von 30 mÄquiv. / kg oder weniger; eine aromatische Carbodiimid-Verbindung und eine Verbindung auf Phosphitbasis,
    wobei der Gehalt der Verbindung auf Phosphitbasis 0,05 Massenteile oder mehr bis 0,12 Massenteile oder weniger pro 100 Massenteile des Polybutylen-Terephthalat-Harzes beträgt.
  2. Polybutylen-Terephthalat-Harzzusammensetzung nach Anspruch 1, wobei der Gehalt der aromatischen Carbodiimid-Verbindung 0,01 Massenteile oder mehr bis 5,0 Massenteile oder weniger pro 100 Massenteile des Polybutylen-Terephthalat-Harzes beträgt.
  3. Polybutylen-Terephthalat-Harzzusammensetzung nach Anspruch 1 oder 2, wobei der Formgegenstand eine Wärmeschock-Beständigkeit von 300 Zyklen oder mehr, wie gemäß einem Wärmeschock-Beständigkeits-Test gemessen, und eine Zunahme des Farbton b*-Wertes um 5 oder weniger vor und nach der Behandlung, wie mit einem Farbdifferenzmesser vor und nach der Kälte- und Wärmebehandlung von 120°C x 1000 Stunden gemessen, aufweist,
    wobei der Wärmeschock-Beständigkeits-Test wie folgt definiert ist:
    ein Zyklus, bei dem der Formgegenstand in einer Kälte- und Wärmeschock-Testmaschine für 1 Stunde und 30 Minuten bei 140°C erhitzt wird, und dann auf -40°C abgekühlt und für 1 Stunde und 30 Minuten gehalten wird, und dann wieder auf 140°C erhitzt wird, um die Anzahl der Zyklen zu bestimmen, bis ein Riss im Formgegenstand auftritt, wodurch die Wärmeschock-Beständigkeit bewertet wird.
  4. Polybutylen-Terephthalat-Harzzusammensetzung nach Anspruch 3, wobei der Formgegenstand einen Farbton b*-Wert von 10 oder weniger aufweist, wie mit einem Farbdifferenzmesser vor und nach der Kalt-Wärme-Behandlung von 120°C x 1000 Stunden gemessen.
EP16859858.9A 2015-10-30 2016-10-26 Polybutylenterephthalat-harzzusammensetzung Active EP3369777B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL16859858T PL3369777T3 (pl) 2015-10-30 2016-10-26 Kompozycja żywicy w postaci poli(tereftalanu butylenu)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015214131 2015-10-30
PCT/JP2016/081763 WO2017073629A1 (ja) 2015-10-30 2016-10-26 ポリブチレンテレフタレート樹脂組成物

Publications (3)

Publication Number Publication Date
EP3369777A1 EP3369777A1 (de) 2018-09-05
EP3369777A4 EP3369777A4 (de) 2018-12-05
EP3369777B1 true EP3369777B1 (de) 2020-05-13

Family

ID=58630509

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16859858.9A Active EP3369777B1 (de) 2015-10-30 2016-10-26 Polybutylenterephthalat-harzzusammensetzung

Country Status (7)

Country Link
US (1) US10526482B2 (de)
EP (1) EP3369777B1 (de)
JP (1) JP6267406B2 (de)
CN (1) CN108350255B (de)
HU (1) HUE050528T2 (de)
PL (1) PL3369777T3 (de)
WO (1) WO2017073629A1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016104201A1 (ja) * 2014-12-26 2016-06-30 ウィンテックポリマー株式会社 ポリアルキレンテレフタレート樹脂組成物
JP6483194B2 (ja) * 2017-06-07 2019-03-13 ウィンテックポリマー株式会社 ポリブチレンテレフタレート樹脂組成物
WO2020080489A1 (ja) * 2018-10-18 2020-04-23 株式会社ダイセル 点火器組立体
JP2020067268A (ja) * 2018-10-18 2020-04-30 株式会社ダイセル 点火器組立体
JPWO2020158903A1 (ja) * 2019-01-30 2021-12-02 三菱エンジニアリングプラスチックス株式会社 粉末積層造形法用の樹脂組成物、ペレット、粉末、造形物の製造方法および造形物
KR20210126058A (ko) * 2019-02-12 2021-10-19 도요보 가부시키가이샤 폴리부틸렌테레프탈레이트 수지 조성물
EP3910000A1 (de) * 2020-05-12 2021-11-17 SHPP Global Technologies B.V. Nachhaltige pbt-zusammensetzungen mit verbesserter farbfähigkeit unter verwendung des verfahrens mit gereinigter terephthalsäure

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5248713A (en) 1990-06-13 1993-09-28 Raychem Corporation Stabilized polymeric compositions
JPH05508179A (ja) 1991-06-14 1993-11-18 レイケム・コーポレイション 安定化された高分子組成物
JP3459711B2 (ja) * 1995-10-27 2003-10-27 帝人株式会社 熱可塑性樹脂組成物
JP2005082642A (ja) * 2003-09-05 2005-03-31 Nisshinbo Ind Inc エステル基を有する樹脂用の耐加水分解安定剤及び熱可塑性樹脂組成物
JP4996843B2 (ja) 2005-10-28 2012-08-08 ポリプラスチックス株式会社 難燃性樹脂組成物
JPWO2007072642A1 (ja) * 2005-12-21 2009-05-28 ダイセル化学工業株式会社 ポリエステル系樹脂組成物及び成形体
JP2008024802A (ja) * 2006-07-20 2008-02-07 Toray Ind Inc 難燃性および色調に優れたポリエステル樹脂組成物
JP6038429B2 (ja) 2008-06-11 2016-12-07 ウィンテックポリマー株式会社 ポリブチレンテレフタレート樹脂組成物及び成形品
CN101463183B (zh) 2008-11-28 2011-07-27 上海锦湖日丽塑料有限公司 一种低雾值聚酯组合物及其制备方法
JP5667377B2 (ja) * 2010-04-14 2015-02-12 帝人株式会社 耐熱劣化性が改良された電線被覆用熱可塑性樹脂組成物
US20140058015A1 (en) 2011-04-26 2014-02-27 Win Tech Polymer Ltd. Insert molded article
JP2015159693A (ja) 2014-02-25 2015-09-03 株式会社豊田自動織機 非接触電力伝送システム及び受電装置
JP2017036442A (ja) * 2015-08-12 2017-02-16 東洋紡株式会社 ポリエステル樹脂組成物、これを含む光反射体用部品および光反射体
SI25085A (sl) 2015-10-27 2017-05-31 Gorenje Gospodinjski Aparati, D.D. Gospodinjski aparat s prikazovalnikom delovanja

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
JPWO2017073629A1 (ja) 2017-10-26
EP3369777A4 (de) 2018-12-05
HUE050528T2 (hu) 2020-12-28
CN108350255A (zh) 2018-07-31
PL3369777T3 (pl) 2020-11-02
US20180319976A1 (en) 2018-11-08
CN108350255B (zh) 2020-02-07
JP6267406B2 (ja) 2018-01-24
WO2017073629A1 (ja) 2017-05-04
US10526482B2 (en) 2020-01-07
EP3369777A1 (de) 2018-09-05

Similar Documents

Publication Publication Date Title
EP3369777B1 (de) Polybutylenterephthalat-harzzusammensetzung
JP5214099B2 (ja) 難燃性ポリブチレンテレフタレート樹脂組成物
EP3067387B1 (de) Thermoplastische formmassen
US7829614B2 (en) Reinforced polyester compositions, methods of manufacture, and articles thereof
EP2370517B1 (de) Verstärkte polyesterzusammensetzungen, herstellungsverfahren und gegenstände daraus
EP3647367B1 (de) Thermoplastische polyesterharzzusammensetzung und formartikel daraus
EP3412724A1 (de) Thermoplastische polyesterharzzusammensetzung und formartikel
EP2977411B1 (de) Halbaromatische polyamidharzzusammensetzung und daraus geformter formkörper
JP5670188B2 (ja) ポリブチレンテレフタレート樹脂組成物及び成形品
CN107922718B (zh) 聚对苯二甲酸丁二醇酯树脂组合物
EP3608366B1 (de) Thermoplastische polyesterharzzusammensetzung und formartikel
EP3310840B1 (de) Polybutylenterephthalat-zusammensetzung mit verbesserter hydrolytischer stabilität
EP3828237A1 (de) Flammhemmende harzzusammensetzung und verfahren zu ihrer herstellung
EP3507330B1 (de) Thermoplastische formmassen
EP2881434A1 (de) Gehäuse für eine elektronische vorrichtung
EP2770027B1 (de) Flammhemmende harzzusammensetzung und schmelzgeformter körper
EP3290470A1 (de) Thermoplastische formmassen
EP2857454B1 (de) Polymilchsäureharzzusammensetzung
WO2014104011A1 (ja) ポリブチレンテレフタレート樹脂組成物
EP4116377A1 (de) Polybutylenterephthalatharzzusammensetzung mit hervorragender flammhemmung und hydrolysebeständigkeit sowie daraus hergestellter formkörper
EP4365226A1 (de) Polybutylenterephthalatharzzusammensetzung, verfahren zur herstellung davon und daraus hergestelltes formprodukt
CN106633682A (zh) 包含纤维增强聚对苯二甲酸乙二醇酯的阻燃性组合物
CN114752200A (zh) 一种耐湿热良加工pc组合物及其制备方法和应用

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180516

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

A4 Supplementary search report drawn up and despatched

Effective date: 20181026

RIC1 Information provided on ipc code assigned before grant

Ipc: C08K 5/524 20060101ALI20181022BHEP

Ipc: C08L 67/02 20060101AFI20181022BHEP

Ipc: C08K 5/29 20060101ALI20181022BHEP

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20190712

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20191203

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: POLYPLASTICS CO., LTD.

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016036567

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1270225

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200615

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200513

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200913

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200813

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200814

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200813

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1270225

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200513

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E050528

Country of ref document: HU

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016036567

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20210216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20201026

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201026

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201031

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201026

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201031

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201026

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200513

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: HU

Payment date: 20231024

Year of fee payment: 8

Ref country code: DE

Payment date: 20231020

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20231012

Year of fee payment: 8